Electronic Supplementary Information for Paper

Exceptional adsorption-induced cluster and network deformation in the flexible metal-organic framework DUT-8(Ni)

observed by in situ X-ray diffraction and EXAFS

Volodymyr Bona Nicole Kleinae Irena Senkovskaa Andreas Heerwigaf Juumlrgen Getzschmanna Dirk Wallacherb Ivo Zizakc Maria Brzhezinskayac Uwe Muellerd and Stefan Kaskela

a Inorganic Chemistry I Dresden University of Technology Bergstrasse 66 01069 Dresden Germany Fax +49 (351) 463 37287 E-mail stefankaskelchemietu-dresdendeb Department Sample Environments Helmholtz-Zentrum Berlin fuumlr Materialien und Energie Hahn-Meitner Platz 1 Berlin Germanyc Institute of Nanometer Optics and Technology Helmholtz-Zentrum Berlin fuumlr Materialien und Energie Albert-Einstein-Str 15 12489 Berlin Germanyd Macromolecular Crystallography Group Institute Soft Matter and Functional Materials Helmholtz-Zentrum Berlin fuumlr Materialien und Energie Albert-Einstein-Str 15 12489 Berlin GermanyePresent Address Fraunhofer Institute for Material and Beam Technology IWS Winterbergstraszlige 28 01277 Dresden GermanyfPresent AddressPhysical Chemistry Measurement and Sensor Technology Technische Universitaumlt Dresden Eisenstuckstr 5 01069 Dresden Germany

Content

1 Experimental data for single crystal X-ray diffraction of DUT-8(Ni) cp2 In situ adsorption and X-ray powder diffraction study3 In situ EXAFS measurements during adsorption of N2 at 77 K4 Experimental data and Rietveld plots for DUT-8(Ni) cp phase5 Experimental data and Rietveld plot for C2H6DUT-8(Ni) IP1 phase6 Experimental data and Pawley plot for C2H4DUT-8(Ni) IP2 phase7 Experimental data and Rietveld plot for C2H4DUT-8(Ni) lp phase8 Experimental data and Rietveld plot for N2DUT-8(Ni) lp phase9 Experimental data and Pawley plot for CO2DUT-8(Ni) lp phase10 Experimental data and Pawley plot for C4H10DUT-8(Ni) lp phase11 Phase analysis for in situ adsorption of n-butane (273 K)12 Phase analysis for in situ adsorption of N2 (77 K)13 Phase analysis for in situ adsorption of CO2 (195 K)14 Phase analysis for in situ adsorption of C2H6 (185 K)15 Phase analysis for in situ adsorption of C2H4 (169 K)16 PXRD patterns containing DUT-8(Ni) cp IP1 and C2H6DUT-8(Ni) lp17 PXRD patterns containing DUT-8(Ni) cp IP2 and C2H4DUT-8(Ni) lp18 PXRD patterns containing IP1 and IP2 phases19 PXRD patterns containing DUT-8(Ni) as made (P4n) and N2DUT-8(Ni) (P21m)20 References

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is copy the Owner Societies 2015

1 Experimental data for single crystal X-ray diffraction of DUT-8(Ni) cp

The microcrystal of activated DUT-8(Ni) was glued to the wall of the capillary in inert atmosphere Afterwards the capillary was sealed with wax The data collection was performed at Helmholtz Zentrum Berlin fuumlr Materialien and Energie (MX beamline BL142)1 The synchrotron radiation with energy of 14 kEv (λ = 088561 Aring) was used for the data collection The data were collected at room temperature using φ-scan technique (Δφ = 1deg) Image frames were integrated using the Mosflm 105 software2 Obtained intensities were scaled with the Scala program The crystal structure was solved in P1 space group by direct methods using SHELXTL program package3 Because of poor scattered crystal as well as disorder in the crystal structure only two nickel atoms and their coordination environment could be localized The unit cell parameters are a = 67372(24) Aring b = 80420(28) Aring c = 119468(43) Aring α = 90339(15)deg β = 104014(17)deg γ = 104275(15)deg The atomic coordinates detemined from the single crystal X-ray diffraction measurement are given in Table S1 The organic ligand molecules were simulated using Material Studio 504 Further refinement was performed using X-ray powder diffraction data

Table S1 Atomic coordinates for DUT-8(Ni) cp determined from single crystal X-ray diffraction

Atom x y zNi1 008290 004634 056136Ni2 029973 039539 056838O1 056477 037728 072026O2 031637 005239 071480O3 -007933 017508 047136O4 013056 037830 071343O5 017022 -004104 041704O6 010892 047795 043837O7 039351 023466 044811O8 -010370 007280 067040N1 -017750 -017678 055972N2 059970 057850 048030C1 030911 011455 039112C2 -006967 031070 039334C3 005088 023854 069411

2 In situ adsorption and X-ray powder diffraction study

The sample of DUT-8(Ni) was prepared as described in ref 5 In order to get an optimal grain size for X-ray diffraction the sample was milled in the mortar and sieved using 45 μm sieves The activated sample (20-30 mg) was filled into the sample holder for performing in situ experiments using nitrogen (77 K) n-butane (273 K) carbon dioxide (195 K) ethane (185 K) and ethene (169 K) as probe molecules Measurements were carried out at the MAGS or KMC-2 beamlines at Helmholtz-Zentrum Berlin fuumlr Materialien und Energie (BESSY-II) All experiments were performed using recently constructed sample environment6 The isothermal conditions were created using closed cycle He cryostat The BELSORP-Max automated dosing system ensured the desired gas pressure as well as

connection with the diffractometer All X-ray powder diffraction patterns were collected using the monochromatic radiation with E = 8048 keV (λ = 15406 Aring) in transmission geometry using 2θ scans VAringNTEC-2000 2D area detector from Bruker was used for the collection of diffraction images The image data were integrated using Datasqueeze 22 software7 The phase content in all powder XRD patterns was estimated by the Reference Intensity Ratio method using the Match 111g software8

3 In situ EXAFS measurements during adsorption of N2 at 77 K

The local environment of the Ni atoms was investigated on basis of the X-ray absorption spectra at the Ni K edge (8333 eV) The spectra in the energy range 8200 eV lt E lt 9000 eV were recorded at beamline KMC-2 of Helmholtz-Zentrum Berlin for Materialien und Energie A constant step width of Δk = 005 Aring-1 was used The absorption coefficient μ(E) = -ln(C2C1) of the DUT-8(Ni) sample and the reference (20 μm Ni foil) μref(E)= -ln(C3C2) was calculated from the intensities C1 C2 and C3 detected by ionisation chambers in front and behind the transmitted sample and reference materials 25 mg of activated DUT-8(Ni) was loaded to the sample holder with thickness of 1 mm The latter was put into the adsorption chamber and mounted to the closed cycled He-cryostat The nitrogen adsorption isotherm was measured at 77 K using BELSORP-max automated dosing gas system connected to the adsorption chamber by thin copper capillary The EXAFS spectra were measured at the 5 points of interest

Data processing analyses and fits have been performed with the Demeter software package9 The fits were performed in R-space in the 10 ndash 30 Aring range over k2-weighted FT of the (k) functions performed in the 30-150 Aring-1 interval A single ΔE0 and a single S0

2 have been optimized for all SS (single scattering) paths used in fit Whereas ΔR (change in half path length) and σ2 (Debye-Waller factor) were fitted individually for each scattering pairThe series of electron scattering paths for the first shell of Ni atom were calculated from the crystal structures of both cp and lp phases using FEFF Version 6 of the Artemis software In the case of cp phase the three NimdashO SS paths with similar Ni-O distance were averaged and fitted with degeneracy parameter of 3 in order to increase the dataparameter ratio The SS paths with longer NimdashO distance as well as NimdashN and NimdashNi paths are fitted separately with degeneracy parameter of 1 In the case of N2DUT-8(Ni) lp phase NimdashO and NimdashCcarboxylate paths were fitted with degeneracy parameter of 4 whereas NimdashN and NimdashNi paths were treated the same as in cp phase The result of the fit is given in Table S2

Table S2 Fit parameters for the EXAFS data

Sample conditions DUT-8(Ni) cp DUT-8(Ni) lpTemperature 77 K 77 KR-factor 00089 00094Independent points 14 16Number of variables 10 9S0

2 1385 plusmn 0065 0488 plusmn 0048E0 -13755 plusmn 1324 1378 plusmn 0828RNimdashO1 (Aring)σ2(NimdashO1) (Aring2)

20608 plusmn 0004 (N = 3)-00036 plusmn 00047

2017 plusmn 0007 (N = 4)000068 plusmn 000052

RNimdashO (Aring)σ2(NimdashO2) (Aring2)

1958 plusmn 0019 (N = 1)-00053 plusmn 00031

-

RNimdashN (Aring)σ2(NimdashN) (Aring2)

1895 plusmn 0033 (N = 1)-00026 plusmn 00011

1902 plusmn 0035 (N = 1)00017 plusmn 00014

RNimdashNi (Aring)σ2(NimdashNi) (Aring2)

27591 plusmn 00149 (N = 1)00073 plusmn 00017

2660 plusmn 0015 (N = 1)00055 plusmn 00016

RNimdashC (Aring)σ2(NimdashC) (Aring2)

- 2926 plusmn 0015 (N = 4)00017 plusmn 00014

4 Experimental data and Rietveld plots for DUT-8(Ni) cp phase

The unit cell parameters for the Pawley refinement were taken from the results of single crystal X-ray diffraction measurements on a microcrystal For the refinement of the profile parameters the Thompson-Cox-Hasting function was used The profile asymmetry was corrected using Berrar-Baldinozzi correction After the refinement of the profile the starting model was simulated in the Material Studio 50 visualization tool using the coordinates for the Ni atoms obtained from the single crystal X-ray diffraction study Two structural models in the space groups P1 and P were simulated for the Rietveld refinement Because of 1inappropriate ratio of observed reflectionrsquos intensity in the XRPD to the structural parameters if every atom is considered as independent the rigid body constraints for naphtalene rings carboxylate groups and dabco molecules were used in the refinement The nickel atoms (as main scattering units in the structure) were refined independently The combined Rietveld and energy refinement procedure involving 1 of energy contribution was used Although the centrosymmetric space group would be more appropriate from the symmetry point of view and dataparameters ratio the refinement in the P does not result in the satisfactory fit 1Therefore the structure was refined in the P1 space group with pretty good fit for all of the reflections It should be mentioned that non centrosymmetric space groups are often chosen for the refinement of low symmetrical contracted phases For example the MIL-53(Cr) lt phase was refined in the non centrosymmetric Cc space group although additional crystallographic symmetry is present The detailed path used for the crystal structure solution and refinement is shown in Fig S1

Figure S1 The path used for the structure solution and refinement of DUT-8(Ni) cp

Crystal data for DUT-8(Ni) cp (CuKα1 λ = 15406 Aring) C30H24N2Ni2O8 Mr = 65789 triclinic P1 a = 6947(2) Aring b = 8181(2) Aring c = 12172(3) Aring α = 9114(3)deg β = 10387(4)deg γ = 10455(4)deg V = 6477(2) Aring3 Z = 1 Dc = 1687 g cm-3 3 motion groups 17 degrees of freedom 2θ range 5-50deg Rp = 00434 Rwp = 00628 CCDC-1034317 contains the supplementary crystallographic data for DUT-8(Ni) These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via wwwccdccamacukdata_requestcif Final Rietveld refinement plot is shown in Fig S2

connection with the diffractometer All X-ray powder diffraction patterns were collected using the monochromatic radiation with E = 8048 keV (λ = 15406 Aring) in transmission geometry using 2θ scans VAringNTEC-2000 2D area detector from Bruker was used for the collection of diffraction images The image data were integrated using Datasqueeze 22 software7 The phase content in all powder XRD patterns was estimated by the Reference Intensity Ratio method using the Match 111g software8

3 In situ EXAFS measurements during adsorption of N2 at 77 K

The local environment of the Ni atoms was investigated on basis of the X-ray absorption spectra at the Ni K edge (8333 eV) The spectra in the energy range 8200 eV lt E lt 9000 eV were recorded at beamline KMC-2 of Helmholtz-Zentrum Berlin for Materialien und Energie A constant step width of Δk = 005 Aring-1 was used The absorption coefficient μ(E) = -ln(C2C1) of the DUT-8(Ni) sample and the reference (20 μm Ni foil) μref(E)= -ln(C3C2) was calculated from the intensities C1 C2 and C3 detected by ionisation chambers in front and behind the transmitted sample and reference materials 25 mg of activated DUT-8(Ni) was loaded to the sample holder with thickness of 1 mm The latter was put into the adsorption chamber and mounted to the closed cycled He-cryostat The nitrogen adsorption isotherm was measured at 77 K using BELSORP-max automated dosing gas system connected to the adsorption chamber by thin copper capillary The EXAFS spectra were measured at the 5 points of interest

Data processing analyses and fits have been performed with the Demeter software package9 The fits were performed in R-space in the 10 ndash 30 Aring range over k2-weighted FT of the (k) functions performed in the 30-150 Aring-1 interval A single ΔE0 and a single S0

2 have been optimized for all SS (single scattering) paths used in fit Whereas ΔR (change in half path length) and σ2 (Debye-Waller factor) were fitted individually for each scattering pairThe series of electron scattering paths for the first shell of Ni atom were calculated from the crystal structures of both cp and lp phases using FEFF Version 6 of the Artemis software In the case of cp phase the three NimdashO SS paths with similar Ni-O distance were averaged and fitted with degeneracy parameter of 3 in order to increase the dataparameter ratio The SS paths with longer NimdashO distance as well as NimdashN and NimdashNi paths are fitted separately with degeneracy parameter of 1 In the case of N2DUT-8(Ni) lp phase NimdashO and NimdashCcarboxylate paths were fitted with degeneracy parameter of 4 whereas NimdashN and NimdashNi paths were treated the same as in cp phase The result of the fit is given in Table S2

Table S2 Fit parameters for the EXAFS data

Sample conditions DUT-8(Ni) cp DUT-8(Ni) lpTemperature 77 K 77 KR-factor 00089 00094Independent points 14 16Number of variables 10 9S0

2 1385 plusmn 0065 0488 plusmn 0048E0 -13755 plusmn 1324 1378 plusmn 0828RNimdashO1 (Aring)σ2(NimdashO1) (Aring2)

20608 plusmn 0004 (N = 3)-00036 plusmn 00047

2017 plusmn 0007 (N = 4)000068 plusmn 000052

RNimdashO (Aring)σ2(NimdashO2) (Aring2)

1958 plusmn 0019 (N = 1)-00053 plusmn 00031

-

RNimdashN (Aring)σ2(NimdashN) (Aring2)

1895 plusmn 0033 (N = 1)-00026 plusmn 00011

1902 plusmn 0035 (N = 1)00017 plusmn 00014

RNimdashNi (Aring)σ2(NimdashNi) (Aring2)

27591 plusmn 00149 (N = 1)00073 plusmn 00017

2660 plusmn 0015 (N = 1)00055 plusmn 00016

RNimdashC (Aring)σ2(NimdashC) (Aring2)

- 2926 plusmn 0015 (N = 4)00017 plusmn 00014

4 Experimental data and Rietveld plots for DUT-8(Ni) cp phase

The unit cell parameters for the Pawley refinement were taken from the results of single crystal X-ray diffraction measurements on a microcrystal For the refinement of the profile parameters the Thompson-Cox-Hasting function was used The profile asymmetry was corrected using Berrar-Baldinozzi correction After the refinement of the profile the starting model was simulated in the Material Studio 50 visualization tool using the coordinates for the Ni atoms obtained from the single crystal X-ray diffraction study Two structural models in the space groups P1 and P were simulated for the Rietveld refinement Because of 1inappropriate ratio of observed reflectionrsquos intensity in the XRPD to the structural parameters if every atom is considered as independent the rigid body constraints for naphtalene rings carboxylate groups and dabco molecules were used in the refinement The nickel atoms (as main scattering units in the structure) were refined independently The combined Rietveld and energy refinement procedure involving 1 of energy contribution was used Although the centrosymmetric space group would be more appropriate from the symmetry point of view and dataparameters ratio the refinement in the P does not result in the satisfactory fit 1Therefore the structure was refined in the P1 space group with pretty good fit for all of the reflections It should be mentioned that non centrosymmetric space groups are often chosen for the refinement of low symmetrical contracted phases For example the MIL-53(Cr) lt phase was refined in the non centrosymmetric Cc space group although additional crystallographic symmetry is present The detailed path used for the crystal structure solution and refinement is shown in Fig S1

Figure S1 The path used for the structure solution and refinement of DUT-8(Ni) cp

Crystal data for DUT-8(Ni) cp (CuKα1 λ = 15406 Aring) C30H24N2Ni2O8 Mr = 65789 triclinic P1 a = 6947(2) Aring b = 8181(2) Aring c = 12172(3) Aring α = 9114(3)deg β = 10387(4)deg γ = 10455(4)deg V = 6477(2) Aring3 Z = 1 Dc = 1687 g cm-3 3 motion groups 17 degrees of freedom 2θ range 5-50deg Rp = 00434 Rwp = 00628 CCDC-1034317 contains the supplementary crystallographic data for DUT-8(Ni) These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via wwwccdccamacukdata_requestcif Final Rietveld refinement plot is shown in Fig S2

Table S2 Fit parameters for the EXAFS data

Sample conditions DUT-8(Ni) cp DUT-8(Ni) lpTemperature 77 K 77 KR-factor 00089 00094Independent points 14 16Number of variables 10 9S0

2 1385 plusmn 0065 0488 plusmn 0048E0 -13755 plusmn 1324 1378 plusmn 0828RNimdashO1 (Aring)σ2(NimdashO1) (Aring2)

20608 plusmn 0004 (N = 3)-00036 plusmn 00047

2017 plusmn 0007 (N = 4)000068 plusmn 000052

RNimdashO (Aring)σ2(NimdashO2) (Aring2)

1958 plusmn 0019 (N = 1)-00053 plusmn 00031

-

RNimdashN (Aring)σ2(NimdashN) (Aring2)

1895 plusmn 0033 (N = 1)-00026 plusmn 00011

1902 plusmn 0035 (N = 1)00017 plusmn 00014

RNimdashNi (Aring)σ2(NimdashNi) (Aring2)

27591 plusmn 00149 (N = 1)00073 plusmn 00017

2660 plusmn 0015 (N = 1)00055 plusmn 00016

RNimdashC (Aring)σ2(NimdashC) (Aring2)

- 2926 plusmn 0015 (N = 4)00017 plusmn 00014

4 Experimental data and Rietveld plots for DUT-8(Ni) cp phase

The unit cell parameters for the Pawley refinement were taken from the results of single crystal X-ray diffraction measurements on a microcrystal For the refinement of the profile parameters the Thompson-Cox-Hasting function was used The profile asymmetry was corrected using Berrar-Baldinozzi correction After the refinement of the profile the starting model was simulated in the Material Studio 50 visualization tool using the coordinates for the Ni atoms obtained from the single crystal X-ray diffraction study Two structural models in the space groups P1 and P were simulated for the Rietveld refinement Because of 1inappropriate ratio of observed reflectionrsquos intensity in the XRPD to the structural parameters if every atom is considered as independent the rigid body constraints for naphtalene rings carboxylate groups and dabco molecules were used in the refinement The nickel atoms (as main scattering units in the structure) were refined independently The combined Rietveld and energy refinement procedure involving 1 of energy contribution was used Although the centrosymmetric space group would be more appropriate from the symmetry point of view and dataparameters ratio the refinement in the P does not result in the satisfactory fit 1Therefore the structure was refined in the P1 space group with pretty good fit for all of the reflections It should be mentioned that non centrosymmetric space groups are often chosen for the refinement of low symmetrical contracted phases For example the MIL-53(Cr) lt phase was refined in the non centrosymmetric Cc space group although additional crystallographic symmetry is present The detailed path used for the crystal structure solution and refinement is shown in Fig S1

Figure S1 The path used for the structure solution and refinement of DUT-8(Ni) cp

Crystal data for DUT-8(Ni) cp (CuKα1 λ = 15406 Aring) C30H24N2Ni2O8 Mr = 65789 triclinic P1 a = 6947(2) Aring b = 8181(2) Aring c = 12172(3) Aring α = 9114(3)deg β = 10387(4)deg γ = 10455(4)deg V = 6477(2) Aring3 Z = 1 Dc = 1687 g cm-3 3 motion groups 17 degrees of freedom 2θ range 5-50deg Rp = 00434 Rwp = 00628 CCDC-1034317 contains the supplementary crystallographic data for DUT-8(Ni) These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via wwwccdccamacukdata_requestcif Final Rietveld refinement plot is shown in Fig S2

Figure S1 The path used for the structure solution and refinement of DUT-8(Ni) cp

Crystal data for DUT-8(Ni) cp (CuKα1 λ = 15406 Aring) C30H24N2Ni2O8 Mr = 65789 triclinic P1 a = 6947(2) Aring b = 8181(2) Aring c = 12172(3) Aring α = 9114(3)deg β = 10387(4)deg γ = 10455(4)deg V = 6477(2) Aring3 Z = 1 Dc = 1687 g cm-3 3 motion groups 17 degrees of freedom 2θ range 5-50deg Rp = 00434 Rwp = 00628 CCDC-1034317 contains the supplementary crystallographic data for DUT-8(Ni) These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via wwwccdccamacukdata_requestcif Final Rietveld refinement plot is shown in Fig S2

Figure S2 Rietveld plot for DUT-8(Ni) cp

5 Experimental data and Rietveld plot for C2H6DUT-8(Ni) IP1 phase

The XRPD measured at pp0 = 061 was used for the pattern indexing procedure performed using Xcell program implemented into the Material Studio 50 package4 From the variety of possible unit cells the write one was chosen after the analysis of figure of merits given by the program in combination with the juxtaposition of the unit cell volume with the cp phase as made phase and correlation with the gas uptake in the isotherm The starting model has been constructed in Material Studio visualizer using P1 unit cell setting with unit cell parameters and atom positions adopted from the cp phase structure The structural model was optimized using geometry optimization tool of Material Studio 50 using Universal Force Field4 The obtained structural model was ldquofilledrdquo with 9 ethane molecules per unit cell (the amount was calculated from the adsorption isotherm) and optimized again The created structural model was subjected to the rigid body Rietveld refinement with energy increment of 2 Naphtalene unit carboxylic groupc dabco molecules and ethylene molecules were refined as rigid bodies Both nickel atoms were refined independently Because of impurity of lp phase the 2θ ranges from 630deg to700deg and from 730deg to 760deg were excluded from the refinement

Crystal data for C2H6DUT-8(Ni) IP1 (synchrotron λ = 15406 Aring) C48H78N2Ni2O8 M = 92850 triclinic P1 a = 9478(1) Aring b = 11066(1) Aring c = 12694(1) Aring α = 10154(1)deg β =

9206(1)deg γ = 10059(1)deg V = 12785(2) Aring3 Z = 1 Dc = 1206 g cm-3 14 motion groups 75 degrees of freedom 2θ range 5-50deg Rp = 01144 Rwp = 01596 CCDC-1034322 contains the supplementary crystallographic data for DUT-8(Ni) These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via wwwccdccamacukdata_requestcif Final Rietveld refinement plot is shown in Fig S3

Figure S3 Rietveld plot for C2H6DUT-8(Ni) IP1

6 Experimental data and Pawley plot for C2H4DUT-8(Ni) IP2 phase

In the case of IP2 phase the indexing of XRPD containing predominantly single IP2 phase was performed using X-Cell utility of Material Studio software The unit cell was chosen using two criteria goodness of fit parameters and crystallographic information available about cp and IP1 phases Unfortunately the quality of XRPD patterns was not sufficient for the Rietveld refinement therefore only Pawley fit of the unit cell is presented Pawley fit data for C2H4DUT-8(Ni) IP2 (synchrotron λ = 15406 Aring) C46H56N2Ni2O8 triclinic P1 a = 9612(1) Aring b = 11254(1) Aring c = 12556(1) Aring α = 10350(1)deg β = 9453(1)deg γ = 9833(1)deg V = 12978(2) Aring3 U = 2144 plusmn 0168 V = -0443 plusmn 0031 W = 00237 plusmn 0002 X = 0471 plusmn 0042 Y = 00533 plusmn 0003 Zero shift -000104 Berar-Baldinozzi asymmetry correction P1 = 3308 P2 = 0647 P3 = -6676 P4 = -1307 2θ range 5-50deg Rp = 1062 Rwp = 1701 Final Pawley refinement plot is shown in Fig S4

9206(1)deg γ = 10059(1)deg V = 12785(2) Aring3 Z = 1 Dc = 1206 g cm-3 14 motion groups 75 degrees of freedom 2θ range 5-50deg Rp = 01144 Rwp = 01596 CCDC-1034322 contains the supplementary crystallographic data for DUT-8(Ni) These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via wwwccdccamacukdata_requestcif Final Rietveld refinement plot is shown in Fig S3

Figure S3 Rietveld plot for C2H6DUT-8(Ni) IP1

6 Experimental data and Pawley plot for C2H4DUT-8(Ni) IP2 phase

In the case of IP2 phase the indexing of XRPD containing predominantly single IP2 phase was performed using X-Cell utility of Material Studio software The unit cell was chosen using two criteria goodness of fit parameters and crystallographic information available about cp and IP1 phases Unfortunately the quality of XRPD patterns was not sufficient for the Rietveld refinement therefore only Pawley fit of the unit cell is presented Pawley fit data for C2H4DUT-8(Ni) IP2 (synchrotron λ = 15406 Aring) C46H56N2Ni2O8 triclinic P1 a = 9612(1) Aring b = 11254(1) Aring c = 12556(1) Aring α = 10350(1)deg β = 9453(1)deg γ = 9833(1)deg V = 12978(2) Aring3 U = 2144 plusmn 0168 V = -0443 plusmn 0031 W = 00237 plusmn 0002 X = 0471 plusmn 0042 Y = 00533 plusmn 0003 Zero shift -000104 Berar-Baldinozzi asymmetry correction P1 = 3308 P2 = 0647 P3 = -6676 P4 = -1307 2θ range 5-50deg Rp = 1062 Rwp = 1701 Final Pawley refinement plot is shown in Fig S4

Figure S4 Pawley plot for C2H4DUT-8(Ni) IP2

7 Experimental data and Rietveld plot for C2H4DUT-8(Ni) lp phase

Since the XRD pattern of C2H4DUT-8(Ni) phase at pp0 = 092 does not match the theoretical patterns of ldquoas maderdquo DUT-8(Ni) the pattern was indexed using Xcell program in Material Studio 504 The best match was obtained for the monoclinic unit cell with the unit cell parameters and cell volume very similar to the cell parameters of as made tetragonal phase (monoclinic angle 94deg) The analysis of the systematic extinctions suggests P21m space group The structural model for the Rietveld refinement was created in Material Studio 50 visualizer using ldquoas maderdquo structure as a starting model4 After optimization of the geometry rigid body Rietveld refinement was performed following the same procedure as it was used for DUT-8(Ni) cp phase with only difference that additional 9 ethylene molecules per paddle-wheel unit were placed into the pore Crystal data for C2H4DUT-8(Ni) lp (synchrotron λ = 15406 Aring) C46H56N2Ni2O89C2H4 M = 105031 monoclinic P21m a = 20405(1) Aring b = 16497(1) Aring c = 9347(1) Aring β = 9412(1)deg V = 31382(1) Aring3 Z = 2 Dc = 1231 g cm-3 16 motion groups 78 degrees of freedom 2θ range 5-50deg Rp = 01101 Rwp = 01471 CCDC-1034320 contains the supplementary crystallographic data for C2H4DUT-8(Ni) lp These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via wwwccdccamacukdata_requestcif Final Rietveld refinement plot is shown in Fig S5

Figure S5 Rietveld plot for C2H4DUT-8(Ni) lp

8 Experimental data and Rietveld plot for N2DUT-8(Ni) lp phase

The powder XRD pattern measured at pp0 = 095 in the in situ adsorption experiment does not match exactly the theoretical patterns of DUT-8(Ni) ldquoas maderdquo phase Therefore the pattern was indexed using Xcell program of Material Studio 504 As in the previous case the indeing results in the monoclinic cell with very similar parameters and volume The starting model for the Rietveld refinement was created in the similar way as described for C2H4DUT-8(Ni) lp model but 15 N2 molecules were added into the pore Because of the cp impurity presented the 2θ range from 73deg to 78deg was excluded from the refinement Crystal data for N2DUT-8(Ni) lp (synchrotron λ = 15406 Aring) C46H56N2Ni2O815N2 M = 130231 monoclinic P21m a = 18657(1) Aring b = 18736(1) Aring c = 9433(1) Aring β = 9442(1)deg V = 32876(1) Aring3 Z = 2 Dc = 1514 g cm-3 21 motion groups 97 degrees of freedom 2θ range 5-50deg Rp = 01450 Rwp = 01837 CCDC-1034323 contains the supplementary crystallographic data for N2DUT-8(Ni) lp These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via wwwccdccamacukdata_requestcif Final Rietveld refinement plot is shown in Fig S6

Figure S6 Rietveld plot for N2DUT-8(Ni) lp

9 Experimental data and Pawley plot for CO2DUT-8(Ni) lp phase

The XRD pattern measured during the in situ adsorption experiment at pp0 = 096 was subjected to the Pawley refinement after the successful indexing performed using Xcell program of Material Studio 50 software Due to the presence of the cp phase impurity the 2θ range from 73deg to 77deg was excluded from the calculations Pawley fit data for CO2DUT-8(Ni) lp (synchrotron λ = 15406 Aring) monoclinic a = 18475(1) Aring b = 18604(1) Aring c = 9431(1) Aring β = 9545(1)deg V = 32269(2) Aring3 U = -0134 plusmn 0036 V = 0089 plusmn 0012 W = -0002 plusmn 0001 X = 0286 plusmn 0029 Y = 0041 plusmn 0002 Zero shift -0012 Berar-Baldinozzi asymmetry correction P1 = 5441 P2 = 0549 P3 = -10883 P4 = -1087 2θ range 5-50deg Rp = 00535 Rwp = 00867 The theoretical pattern was simulated using Material Studio 50 software assuming P21m space group and unit cell parameters obtained from the Pawley refinement Final Pawley refinement plot is shown in Fig S7

Figure S7 Pawley plot for CO2DUT-8(Ni) lp

10 Experimental data and Pawley plot for C4H10DUT-8(Ni) lp phase

The PXRD pattern measured at pp0 = 095 during the in situ adsorption experiment was used for the data analysis As for all previous cases the monoclinic unit cell with cell parameters similar to all others lp phases was chosen The 2θ range 73 ndash 77deg was excluded from the Pawley refinement because of cp phase impurity Pawley fit data for C4H10DUT-8(Ni) lp (synchrotron λ = 15406 Aring) monoclinic a = 18520(1) Aring b = 18191(1) Aring c = 9409(1) Aring β = 9560(1)deg V = 31510(8) Aring3 U = -0262 plusmn 0024 V = 0126 plusmn 0023 W = -00002 X = 0191 plusmn 0013 Y = 0014 plusmn 0001 Z = -0001 Zero shift -00003 Berar-Baldinozzi asymmetry correction P1 = 3114 P2 = 0758 P3 = -6216 P4 = -1515 2θ range 6-50deg Rp = 01127 Rwp = 01597 The theoretical pattern was simulated using Material Studio 50 software assuming P21m space group and unit cell parameters obtained from the Pawley refinement Final Pawley refinement plot is shown in Fig S8

Figure S8 Pawley plot for C4H10DUT-8(Ni) lp

11 Phase analysis for in situ adsorption of n-butane (273K)

Figure S9 In situ-powder XRD during adsorption of n-butane on DUT-8(Ni)

Table S2 Results of phase analysis of powder XRDs for in situ n-butane experiment at 273K

Measuring point DUT-8(Ni) cp DUT-8(Ni) lp 1 99 12 99 13 95 54 80 205 63 376 47 537 33 67

12 Phase analysis for in situ adsorption of N2 (77K)

Figure S10 In situ powder XRD patterns measured during adsorption of N2 (77K) on DUT-8(Ni)

Table S4 Phase analysis of powder XRD patterns collected in situ during N2 adsorption experiment at 77K

Measuring point DUT-8(Ni) cp DUT-8(Ni) lp Evacuated 77 K 98 2

1 99 12 99 13 99 14 25 755 30 706 44 567 46 548 42 589 41 59

Phase analysis for in situ adsorption of CO2 (195 K)

Figure S11 In situ powder XRD patterns measured during adsorption of CO2 (195 K) on DUT-8(Ni)

Table S5 Phase analysis of powder XRD patterns measured during in situ CO2 adsorption experiment at 195K

DUT-8(Ni) cp DUT-8(Ni) lp evacuated 98 2

1 98 22 100 0

3 100 04 98 25 92 86 83 177 69 318 59 419 49 5110 43 5711 41 5912 36 64

13 Phase analysis for in situ adsorption of ethane (185 K)

Figure S12 In situ powder XRD patterns measured during adsorption of ethane (185 K) on DUT-8(Ni)

Table S6 Phase analysis of powder XRD patterns measured in situ during ethane adsorption experiment at 185 K

DUT-8(Ni) cp DUT-8(Ni) IP1 DUT-8(Ni) lp evacuated 98 0 2

1 99 0 12 97 2 13 72 28 04 25 75 05 19 81 06 12 88 07 8 92 08 8 92 09 6 88 610 3 87 1011 0 85 1512 0 74 2613 0 64 36

14 Phase analysis for in situ adsorption of ethene (169K)

Figure S13 In situ powder XRD patterns measured during adsorption of ethane (169 K) on DUT-8(Ni)

Table S7 Phase analysis of powder XRD patterns measured during in situ ethene adsorption experiment at 169K

Measuring point DUT-8(Ni) cp DUT-8(Ni) IP2 DUT-8(Ni) lp 1 98 0 22 99 0 13 99 0 14 99 0 15 87 12 16 86 13 17 46 53 18 0 71 299 0 71 2910 0 40 6011 0 38 6212 0 33 6713 0 32 6814 0 0 10015 0 96 416 0 98 217 0 99 118 0 99 1

15 PXRDs containing DUT-8(Ni) cp IP1 and C2H6DUT-8(Ni) lp

Figure S14 Experimental PXRD patterns measured during adsorption of ethane at 185 K in blue ndash XRD at pp0 =021 (DUT-8(Ni) cp) in red XRD at pp0 = 061 (IP1) in light green XRD at pp0 = 099 (mixture of C2H6DUT-8(Ni) lp and IP1)

16 PXRDs containing DUT-8(Ni) cp IP2 and C2H4DUT-8(Ni) lp

Figure S15 Experimental XRD patterns measured during adsorption of ethane at 169 K in blue XRD at pp0 = 011 (DUT-8(Ni) cp) in red XRD at pp0 = 0008 (desorption) (IP2) in light green XRD at pp0 = 092 (adsorption) (C2H4DUT-8(Ni) lp)

17 PXRDs containing IP1 and IP2 phases

Figure S16 Experimental XRD patterns of IP1 measured at pp0 = 061 185 K (ethane adsorption 185 K) in blue and of IP2 measured at pp0 = 0008 (ethylene desorption 169 K) in red

18 PXRDs containing DUT-8(Ni) as made (P4n) and N2DUT-8(Ni) (P21m)

Figure S17 Theoretical PXRD pattern of ldquoas maderdquo DUT-8(Ni) (green) experimental PXRD pattern of ldquoas maderdquo DUT-8(Ni) (blue) theoretical PXRD pattern of N2DUT-8(Ni) lp (violet) experimental PXRD pattern of N2DUT-8(Ni) lp measured at pp0 = 095 and 77K (red) (Reflection marked with asterisk belongs to the DUT-8(Ni) cp phase)

19 References

1 U Mueller N Darowski M R Fuchs R Forster M Hellmig K S Paithankar S Puhringer M Steffien G Zocher and M S Weiss J Synchrotron Rad 2012 19 442-449

2 M D Winn C C Ballard K D Cowtan E J Dodson P Emsley P R Evans R M Keegan E B Krissinel A G W Leslie A McCoy S J McNicholas G N Murshudov N S Pannu E A Potterton H R Powell R J Read A Vagin and K S Wilson Acta Cryst D 2011 67 235-242

3 G Sheldrick Acta Cryst A 2008 64 112-1224 in Material Studio Accelrys Software Inc San Diego Release 50 edn 20095 N Klein C Herzog M Sabo I Senkovska J Getzschmann S Paasch M R Lohe

E Brunner and S Kaskel Phys Chem Chem Phys 2010 12 11778-117846 V Bon I Senkovska D Wallacher A Heerwig N Klein I Zizak R Feyerherm E

Dudzik and S Kaskel Micropor Mesopor Mat 20147 P Heiney University of Pennsylvania 223 edn 20108 H P K Brandenburg Crystal Impact 111g edn 20149 B Ravel and M Newville J Synchrotron Rad 2005 12 537-541

Figure S7 Pawley plot for CO2DUT-8(Ni) lp

10 Experimental data and Pawley plot for C4H10DUT-8(Ni) lp phase

The PXRD pattern measured at pp0 = 095 during the in situ adsorption experiment was used for the data analysis As for all previous cases the monoclinic unit cell with cell parameters similar to all others lp phases was chosen The 2θ range 73 ndash 77deg was excluded from the Pawley refinement because of cp phase impurity Pawley fit data for C4H10DUT-8(Ni) lp (synchrotron λ = 15406 Aring) monoclinic a = 18520(1) Aring b = 18191(1) Aring c = 9409(1) Aring β = 9560(1)deg V = 31510(8) Aring3 U = -0262 plusmn 0024 V = 0126 plusmn 0023 W = -00002 X = 0191 plusmn 0013 Y = 0014 plusmn 0001 Z = -0001 Zero shift -00003 Berar-Baldinozzi asymmetry correction P1 = 3114 P2 = 0758 P3 = -6216 P4 = -1515 2θ range 6-50deg Rp = 01127 Rwp = 01597 The theoretical pattern was simulated using Material Studio 50 software assuming P21m space group and unit cell parameters obtained from the Pawley refinement Final Pawley refinement plot is shown in Fig S8

Figure S8 Pawley plot for C4H10DUT-8(Ni) lp

11 Phase analysis for in situ adsorption of n-butane (273K)

Figure S9 In situ-powder XRD during adsorption of n-butane on DUT-8(Ni)

Table S2 Results of phase analysis of powder XRDs for in situ n-butane experiment at 273K

Measuring point DUT-8(Ni) cp DUT-8(Ni) lp 1 99 12 99 13 95 54 80 205 63 376 47 537 33 67

12 Phase analysis for in situ adsorption of N2 (77K)

Figure S10 In situ powder XRD patterns measured during adsorption of N2 (77K) on DUT-8(Ni)

Table S4 Phase analysis of powder XRD patterns collected in situ during N2 adsorption experiment at 77K

Measuring point DUT-8(Ni) cp DUT-8(Ni) lp Evacuated 77 K 98 2

1 99 12 99 13 99 14 25 755 30 706 44 567 46 548 42 589 41 59

Phase analysis for in situ adsorption of CO2 (195 K)

Figure S11 In situ powder XRD patterns measured during adsorption of CO2 (195 K) on DUT-8(Ni)

Table S5 Phase analysis of powder XRD patterns measured during in situ CO2 adsorption experiment at 195K

DUT-8(Ni) cp DUT-8(Ni) lp evacuated 98 2

1 98 22 100 0

3 100 04 98 25 92 86 83 177 69 318 59 419 49 5110 43 5711 41 5912 36 64

13 Phase analysis for in situ adsorption of ethane (185 K)

Figure S12 In situ powder XRD patterns measured during adsorption of ethane (185 K) on DUT-8(Ni)

Table S6 Phase analysis of powder XRD patterns measured in situ during ethane adsorption experiment at 185 K

DUT-8(Ni) cp DUT-8(Ni) IP1 DUT-8(Ni) lp evacuated 98 0 2

1 99 0 12 97 2 13 72 28 04 25 75 05 19 81 06 12 88 07 8 92 08 8 92 09 6 88 610 3 87 1011 0 85 1512 0 74 2613 0 64 36

14 Phase analysis for in situ adsorption of ethene (169K)

Figure S13 In situ powder XRD patterns measured during adsorption of ethane (169 K) on DUT-8(Ni)

Table S7 Phase analysis of powder XRD patterns measured during in situ ethene adsorption experiment at 169K

Measuring point DUT-8(Ni) cp DUT-8(Ni) IP2 DUT-8(Ni) lp 1 98 0 22 99 0 13 99 0 14 99 0 15 87 12 16 86 13 17 46 53 18 0 71 299 0 71 2910 0 40 6011 0 38 6212 0 33 6713 0 32 6814 0 0 10015 0 96 416 0 98 217 0 99 118 0 99 1

15 PXRDs containing DUT-8(Ni) cp IP1 and C2H6DUT-8(Ni) lp

Figure S14 Experimental PXRD patterns measured during adsorption of ethane at 185 K in blue ndash XRD at pp0 =021 (DUT-8(Ni) cp) in red XRD at pp0 = 061 (IP1) in light green XRD at pp0 = 099 (mixture of C2H6DUT-8(Ni) lp and IP1)

16 PXRDs containing DUT-8(Ni) cp IP2 and C2H4DUT-8(Ni) lp

Figure S15 Experimental XRD patterns measured during adsorption of ethane at 169 K in blue XRD at pp0 = 011 (DUT-8(Ni) cp) in red XRD at pp0 = 0008 (desorption) (IP2) in light green XRD at pp0 = 092 (adsorption) (C2H4DUT-8(Ni) lp)

17 PXRDs containing IP1 and IP2 phases

Figure S16 Experimental XRD patterns of IP1 measured at pp0 = 061 185 K (ethane adsorption 185 K) in blue and of IP2 measured at pp0 = 0008 (ethylene desorption 169 K) in red

18 PXRDs containing DUT-8(Ni) as made (P4n) and N2DUT-8(Ni) (P21m)

Figure S17 Theoretical PXRD pattern of ldquoas maderdquo DUT-8(Ni) (green) experimental PXRD pattern of ldquoas maderdquo DUT-8(Ni) (blue) theoretical PXRD pattern of N2DUT-8(Ni) lp (violet) experimental PXRD pattern of N2DUT-8(Ni) lp measured at pp0 = 095 and 77K (red) (Reflection marked with asterisk belongs to the DUT-8(Ni) cp phase)

19 References

1 U Mueller N Darowski M R Fuchs R Forster M Hellmig K S Paithankar S Puhringer M Steffien G Zocher and M S Weiss J Synchrotron Rad 2012 19 442-449

2 M D Winn C C Ballard K D Cowtan E J Dodson P Emsley P R Evans R M Keegan E B Krissinel A G W Leslie A McCoy S J McNicholas G N Murshudov N S Pannu E A Potterton H R Powell R J Read A Vagin and K S Wilson Acta Cryst D 2011 67 235-242

3 G Sheldrick Acta Cryst A 2008 64 112-1224 in Material Studio Accelrys Software Inc San Diego Release 50 edn 20095 N Klein C Herzog M Sabo I Senkovska J Getzschmann S Paasch M R Lohe

E Brunner and S Kaskel Phys Chem Chem Phys 2010 12 11778-117846 V Bon I Senkovska D Wallacher A Heerwig N Klein I Zizak R Feyerherm E

Dudzik and S Kaskel Micropor Mesopor Mat 20147 P Heiney University of Pennsylvania 223 edn 20108 H P K Brandenburg Crystal Impact 111g edn 20149 B Ravel and M Newville J Synchrotron Rad 2005 12 537-541

Figure S8 Pawley plot for C4H10DUT-8(Ni) lp

11 Phase analysis for in situ adsorption of n-butane (273K)

Figure S9 In situ-powder XRD during adsorption of n-butane on DUT-8(Ni)

Table S2 Results of phase analysis of powder XRDs for in situ n-butane experiment at 273K

Measuring point DUT-8(Ni) cp DUT-8(Ni) lp 1 99 12 99 13 95 54 80 205 63 376 47 537 33 67

12 Phase analysis for in situ adsorption of N2 (77K)

Figure S10 In situ powder XRD patterns measured during adsorption of N2 (77K) on DUT-8(Ni)

Table S4 Phase analysis of powder XRD patterns collected in situ during N2 adsorption experiment at 77K

Measuring point DUT-8(Ni) cp DUT-8(Ni) lp Evacuated 77 K 98 2

1 99 12 99 13 99 14 25 755 30 706 44 567 46 548 42 589 41 59

Phase analysis for in situ adsorption of CO2 (195 K)

Figure S11 In situ powder XRD patterns measured during adsorption of CO2 (195 K) on DUT-8(Ni)

Table S5 Phase analysis of powder XRD patterns measured during in situ CO2 adsorption experiment at 195K

DUT-8(Ni) cp DUT-8(Ni) lp evacuated 98 2

1 98 22 100 0

3 100 04 98 25 92 86 83 177 69 318 59 419 49 5110 43 5711 41 5912 36 64

13 Phase analysis for in situ adsorption of ethane (185 K)

Figure S12 In situ powder XRD patterns measured during adsorption of ethane (185 K) on DUT-8(Ni)

Table S6 Phase analysis of powder XRD patterns measured in situ during ethane adsorption experiment at 185 K

DUT-8(Ni) cp DUT-8(Ni) IP1 DUT-8(Ni) lp evacuated 98 0 2

1 99 0 12 97 2 13 72 28 04 25 75 05 19 81 06 12 88 07 8 92 08 8 92 09 6 88 610 3 87 1011 0 85 1512 0 74 2613 0 64 36

14 Phase analysis for in situ adsorption of ethene (169K)

Figure S13 In situ powder XRD patterns measured during adsorption of ethane (169 K) on DUT-8(Ni)

Table S7 Phase analysis of powder XRD patterns measured during in situ ethene adsorption experiment at 169K

Measuring point DUT-8(Ni) cp DUT-8(Ni) IP2 DUT-8(Ni) lp 1 98 0 22 99 0 13 99 0 14 99 0 15 87 12 16 86 13 17 46 53 18 0 71 299 0 71 2910 0 40 6011 0 38 6212 0 33 6713 0 32 6814 0 0 10015 0 96 416 0 98 217 0 99 118 0 99 1

15 PXRDs containing DUT-8(Ni) cp IP1 and C2H6DUT-8(Ni) lp

Figure S14 Experimental PXRD patterns measured during adsorption of ethane at 185 K in blue ndash XRD at pp0 =021 (DUT-8(Ni) cp) in red XRD at pp0 = 061 (IP1) in light green XRD at pp0 = 099 (mixture of C2H6DUT-8(Ni) lp and IP1)

16 PXRDs containing DUT-8(Ni) cp IP2 and C2H4DUT-8(Ni) lp

Figure S15 Experimental XRD patterns measured during adsorption of ethane at 169 K in blue XRD at pp0 = 011 (DUT-8(Ni) cp) in red XRD at pp0 = 0008 (desorption) (IP2) in light green XRD at pp0 = 092 (adsorption) (C2H4DUT-8(Ni) lp)

17 PXRDs containing IP1 and IP2 phases

Figure S16 Experimental XRD patterns of IP1 measured at pp0 = 061 185 K (ethane adsorption 185 K) in blue and of IP2 measured at pp0 = 0008 (ethylene desorption 169 K) in red

18 PXRDs containing DUT-8(Ni) as made (P4n) and N2DUT-8(Ni) (P21m)

Figure S17 Theoretical PXRD pattern of ldquoas maderdquo DUT-8(Ni) (green) experimental PXRD pattern of ldquoas maderdquo DUT-8(Ni) (blue) theoretical PXRD pattern of N2DUT-8(Ni) lp (violet) experimental PXRD pattern of N2DUT-8(Ni) lp measured at pp0 = 095 and 77K (red) (Reflection marked with asterisk belongs to the DUT-8(Ni) cp phase)

19 References

1 U Mueller N Darowski M R Fuchs R Forster M Hellmig K S Paithankar S Puhringer M Steffien G Zocher and M S Weiss J Synchrotron Rad 2012 19 442-449

2 M D Winn C C Ballard K D Cowtan E J Dodson P Emsley P R Evans R M Keegan E B Krissinel A G W Leslie A McCoy S J McNicholas G N Murshudov N S Pannu E A Potterton H R Powell R J Read A Vagin and K S Wilson Acta Cryst D 2011 67 235-242

3 G Sheldrick Acta Cryst A 2008 64 112-1224 in Material Studio Accelrys Software Inc San Diego Release 50 edn 20095 N Klein C Herzog M Sabo I Senkovska J Getzschmann S Paasch M R Lohe

E Brunner and S Kaskel Phys Chem Chem Phys 2010 12 11778-117846 V Bon I Senkovska D Wallacher A Heerwig N Klein I Zizak R Feyerherm E

Dudzik and S Kaskel Micropor Mesopor Mat 20147 P Heiney University of Pennsylvania 223 edn 20108 H P K Brandenburg Crystal Impact 111g edn 20149 B Ravel and M Newville J Synchrotron Rad 2005 12 537-541

11 Phase analysis for in situ adsorption of n-butane (273K)

Figure S9 In situ-powder XRD during adsorption of n-butane on DUT-8(Ni)

Table S2 Results of phase analysis of powder XRDs for in situ n-butane experiment at 273K

Measuring point DUT-8(Ni) cp DUT-8(Ni) lp 1 99 12 99 13 95 54 80 205 63 376 47 537 33 67

12 Phase analysis for in situ adsorption of N2 (77K)

Figure S10 In situ powder XRD patterns measured during adsorption of N2 (77K) on DUT-8(Ni)

Table S4 Phase analysis of powder XRD patterns collected in situ during N2 adsorption experiment at 77K

Measuring point DUT-8(Ni) cp DUT-8(Ni) lp Evacuated 77 K 98 2

1 99 12 99 13 99 14 25 755 30 706 44 567 46 548 42 589 41 59

Phase analysis for in situ adsorption of CO2 (195 K)

Figure S11 In situ powder XRD patterns measured during adsorption of CO2 (195 K) on DUT-8(Ni)

Table S5 Phase analysis of powder XRD patterns measured during in situ CO2 adsorption experiment at 195K

DUT-8(Ni) cp DUT-8(Ni) lp evacuated 98 2

1 98 22 100 0

3 100 04 98 25 92 86 83 177 69 318 59 419 49 5110 43 5711 41 5912 36 64

13 Phase analysis for in situ adsorption of ethane (185 K)

Figure S12 In situ powder XRD patterns measured during adsorption of ethane (185 K) on DUT-8(Ni)

Table S6 Phase analysis of powder XRD patterns measured in situ during ethane adsorption experiment at 185 K

DUT-8(Ni) cp DUT-8(Ni) IP1 DUT-8(Ni) lp evacuated 98 0 2

1 99 0 12 97 2 13 72 28 04 25 75 05 19 81 06 12 88 07 8 92 08 8 92 09 6 88 610 3 87 1011 0 85 1512 0 74 2613 0 64 36

14 Phase analysis for in situ adsorption of ethene (169K)

Figure S13 In situ powder XRD patterns measured during adsorption of ethane (169 K) on DUT-8(Ni)

Table S7 Phase analysis of powder XRD patterns measured during in situ ethene adsorption experiment at 169K

Measuring point DUT-8(Ni) cp DUT-8(Ni) IP2 DUT-8(Ni) lp 1 98 0 22 99 0 13 99 0 14 99 0 15 87 12 16 86 13 17 46 53 18 0 71 299 0 71 2910 0 40 6011 0 38 6212 0 33 6713 0 32 6814 0 0 10015 0 96 416 0 98 217 0 99 118 0 99 1

15 PXRDs containing DUT-8(Ni) cp IP1 and C2H6DUT-8(Ni) lp

Figure S14 Experimental PXRD patterns measured during adsorption of ethane at 185 K in blue ndash XRD at pp0 =021 (DUT-8(Ni) cp) in red XRD at pp0 = 061 (IP1) in light green XRD at pp0 = 099 (mixture of C2H6DUT-8(Ni) lp and IP1)

16 PXRDs containing DUT-8(Ni) cp IP2 and C2H4DUT-8(Ni) lp

Figure S15 Experimental XRD patterns measured during adsorption of ethane at 169 K in blue XRD at pp0 = 011 (DUT-8(Ni) cp) in red XRD at pp0 = 0008 (desorption) (IP2) in light green XRD at pp0 = 092 (adsorption) (C2H4DUT-8(Ni) lp)

17 PXRDs containing IP1 and IP2 phases

Figure S16 Experimental XRD patterns of IP1 measured at pp0 = 061 185 K (ethane adsorption 185 K) in blue and of IP2 measured at pp0 = 0008 (ethylene desorption 169 K) in red

18 PXRDs containing DUT-8(Ni) as made (P4n) and N2DUT-8(Ni) (P21m)

Figure S17 Theoretical PXRD pattern of ldquoas maderdquo DUT-8(Ni) (green) experimental PXRD pattern of ldquoas maderdquo DUT-8(Ni) (blue) theoretical PXRD pattern of N2DUT-8(Ni) lp (violet) experimental PXRD pattern of N2DUT-8(Ni) lp measured at pp0 = 095 and 77K (red) (Reflection marked with asterisk belongs to the DUT-8(Ni) cp phase)

19 References

1 U Mueller N Darowski M R Fuchs R Forster M Hellmig K S Paithankar S Puhringer M Steffien G Zocher and M S Weiss J Synchrotron Rad 2012 19 442-449

2 M D Winn C C Ballard K D Cowtan E J Dodson P Emsley P R Evans R M Keegan E B Krissinel A G W Leslie A McCoy S J McNicholas G N Murshudov N S Pannu E A Potterton H R Powell R J Read A Vagin and K S Wilson Acta Cryst D 2011 67 235-242

3 G Sheldrick Acta Cryst A 2008 64 112-1224 in Material Studio Accelrys Software Inc San Diego Release 50 edn 20095 N Klein C Herzog M Sabo I Senkovska J Getzschmann S Paasch M R Lohe

E Brunner and S Kaskel Phys Chem Chem Phys 2010 12 11778-117846 V Bon I Senkovska D Wallacher A Heerwig N Klein I Zizak R Feyerherm E

Dudzik and S Kaskel Micropor Mesopor Mat 20147 P Heiney University of Pennsylvania 223 edn 20108 H P K Brandenburg Crystal Impact 111g edn 20149 B Ravel and M Newville J Synchrotron Rad 2005 12 537-541

12 Phase analysis for in situ adsorption of N2 (77K)

Figure S10 In situ powder XRD patterns measured during adsorption of N2 (77K) on DUT-8(Ni)

Table S4 Phase analysis of powder XRD patterns collected in situ during N2 adsorption experiment at 77K

Measuring point DUT-8(Ni) cp DUT-8(Ni) lp Evacuated 77 K 98 2

1 99 12 99 13 99 14 25 755 30 706 44 567 46 548 42 589 41 59

Phase analysis for in situ adsorption of CO2 (195 K)

Figure S11 In situ powder XRD patterns measured during adsorption of CO2 (195 K) on DUT-8(Ni)

Table S5 Phase analysis of powder XRD patterns measured during in situ CO2 adsorption experiment at 195K

DUT-8(Ni) cp DUT-8(Ni) lp evacuated 98 2

1 98 22 100 0

3 100 04 98 25 92 86 83 177 69 318 59 419 49 5110 43 5711 41 5912 36 64

13 Phase analysis for in situ adsorption of ethane (185 K)

Figure S12 In situ powder XRD patterns measured during adsorption of ethane (185 K) on DUT-8(Ni)

Table S6 Phase analysis of powder XRD patterns measured in situ during ethane adsorption experiment at 185 K

DUT-8(Ni) cp DUT-8(Ni) IP1 DUT-8(Ni) lp evacuated 98 0 2

1 99 0 12 97 2 13 72 28 04 25 75 05 19 81 06 12 88 07 8 92 08 8 92 09 6 88 610 3 87 1011 0 85 1512 0 74 2613 0 64 36

14 Phase analysis for in situ adsorption of ethene (169K)

Figure S13 In situ powder XRD patterns measured during adsorption of ethane (169 K) on DUT-8(Ni)

Table S7 Phase analysis of powder XRD patterns measured during in situ ethene adsorption experiment at 169K

Measuring point DUT-8(Ni) cp DUT-8(Ni) IP2 DUT-8(Ni) lp 1 98 0 22 99 0 13 99 0 14 99 0 15 87 12 16 86 13 17 46 53 18 0 71 299 0 71 2910 0 40 6011 0 38 6212 0 33 6713 0 32 6814 0 0 10015 0 96 416 0 98 217 0 99 118 0 99 1

15 PXRDs containing DUT-8(Ni) cp IP1 and C2H6DUT-8(Ni) lp

Figure S14 Experimental PXRD patterns measured during adsorption of ethane at 185 K in blue ndash XRD at pp0 =021 (DUT-8(Ni) cp) in red XRD at pp0 = 061 (IP1) in light green XRD at pp0 = 099 (mixture of C2H6DUT-8(Ni) lp and IP1)

16 PXRDs containing DUT-8(Ni) cp IP2 and C2H4DUT-8(Ni) lp

Figure S15 Experimental XRD patterns measured during adsorption of ethane at 169 K in blue XRD at pp0 = 011 (DUT-8(Ni) cp) in red XRD at pp0 = 0008 (desorption) (IP2) in light green XRD at pp0 = 092 (adsorption) (C2H4DUT-8(Ni) lp)

17 PXRDs containing IP1 and IP2 phases

Figure S16 Experimental XRD patterns of IP1 measured at pp0 = 061 185 K (ethane adsorption 185 K) in blue and of IP2 measured at pp0 = 0008 (ethylene desorption 169 K) in red

18 PXRDs containing DUT-8(Ni) as made (P4n) and N2DUT-8(Ni) (P21m)

Figure S17 Theoretical PXRD pattern of ldquoas maderdquo DUT-8(Ni) (green) experimental PXRD pattern of ldquoas maderdquo DUT-8(Ni) (blue) theoretical PXRD pattern of N2DUT-8(Ni) lp (violet) experimental PXRD pattern of N2DUT-8(Ni) lp measured at pp0 = 095 and 77K (red) (Reflection marked with asterisk belongs to the DUT-8(Ni) cp phase)

19 References

1 U Mueller N Darowski M R Fuchs R Forster M Hellmig K S Paithankar S Puhringer M Steffien G Zocher and M S Weiss J Synchrotron Rad 2012 19 442-449

2 M D Winn C C Ballard K D Cowtan E J Dodson P Emsley P R Evans R M Keegan E B Krissinel A G W Leslie A McCoy S J McNicholas G N Murshudov N S Pannu E A Potterton H R Powell R J Read A Vagin and K S Wilson Acta Cryst D 2011 67 235-242

3 G Sheldrick Acta Cryst A 2008 64 112-1224 in Material Studio Accelrys Software Inc San Diego Release 50 edn 20095 N Klein C Herzog M Sabo I Senkovska J Getzschmann S Paasch M R Lohe

E Brunner and S Kaskel Phys Chem Chem Phys 2010 12 11778-117846 V Bon I Senkovska D Wallacher A Heerwig N Klein I Zizak R Feyerherm E

Dudzik and S Kaskel Micropor Mesopor Mat 20147 P Heiney University of Pennsylvania 223 edn 20108 H P K Brandenburg Crystal Impact 111g edn 20149 B Ravel and M Newville J Synchrotron Rad 2005 12 537-541

Phase analysis for in situ adsorption of CO2 (195 K)

Figure S11 In situ powder XRD patterns measured during adsorption of CO2 (195 K) on DUT-8(Ni)

Table S5 Phase analysis of powder XRD patterns measured during in situ CO2 adsorption experiment at 195K

DUT-8(Ni) cp DUT-8(Ni) lp evacuated 98 2

1 98 22 100 0

3 100 04 98 25 92 86 83 177 69 318 59 419 49 5110 43 5711 41 5912 36 64

13 Phase analysis for in situ adsorption of ethane (185 K)

Figure S12 In situ powder XRD patterns measured during adsorption of ethane (185 K) on DUT-8(Ni)

Table S6 Phase analysis of powder XRD patterns measured in situ during ethane adsorption experiment at 185 K

DUT-8(Ni) cp DUT-8(Ni) IP1 DUT-8(Ni) lp evacuated 98 0 2

1 99 0 12 97 2 13 72 28 04 25 75 05 19 81 06 12 88 07 8 92 08 8 92 09 6 88 610 3 87 1011 0 85 1512 0 74 2613 0 64 36

14 Phase analysis for in situ adsorption of ethene (169K)

Figure S13 In situ powder XRD patterns measured during adsorption of ethane (169 K) on DUT-8(Ni)

Table S7 Phase analysis of powder XRD patterns measured during in situ ethene adsorption experiment at 169K

Measuring point DUT-8(Ni) cp DUT-8(Ni) IP2 DUT-8(Ni) lp 1 98 0 22 99 0 13 99 0 14 99 0 15 87 12 16 86 13 17 46 53 18 0 71 299 0 71 2910 0 40 6011 0 38 6212 0 33 6713 0 32 6814 0 0 10015 0 96 416 0 98 217 0 99 118 0 99 1

15 PXRDs containing DUT-8(Ni) cp IP1 and C2H6DUT-8(Ni) lp

Figure S14 Experimental PXRD patterns measured during adsorption of ethane at 185 K in blue ndash XRD at pp0 =021 (DUT-8(Ni) cp) in red XRD at pp0 = 061 (IP1) in light green XRD at pp0 = 099 (mixture of C2H6DUT-8(Ni) lp and IP1)

16 PXRDs containing DUT-8(Ni) cp IP2 and C2H4DUT-8(Ni) lp

Figure S15 Experimental XRD patterns measured during adsorption of ethane at 169 K in blue XRD at pp0 = 011 (DUT-8(Ni) cp) in red XRD at pp0 = 0008 (desorption) (IP2) in light green XRD at pp0 = 092 (adsorption) (C2H4DUT-8(Ni) lp)

17 PXRDs containing IP1 and IP2 phases

Figure S16 Experimental XRD patterns of IP1 measured at pp0 = 061 185 K (ethane adsorption 185 K) in blue and of IP2 measured at pp0 = 0008 (ethylene desorption 169 K) in red

18 PXRDs containing DUT-8(Ni) as made (P4n) and N2DUT-8(Ni) (P21m)

Figure S17 Theoretical PXRD pattern of ldquoas maderdquo DUT-8(Ni) (green) experimental PXRD pattern of ldquoas maderdquo DUT-8(Ni) (blue) theoretical PXRD pattern of N2DUT-8(Ni) lp (violet) experimental PXRD pattern of N2DUT-8(Ni) lp measured at pp0 = 095 and 77K (red) (Reflection marked with asterisk belongs to the DUT-8(Ni) cp phase)

19 References

1 U Mueller N Darowski M R Fuchs R Forster M Hellmig K S Paithankar S Puhringer M Steffien G Zocher and M S Weiss J Synchrotron Rad 2012 19 442-449

2 M D Winn C C Ballard K D Cowtan E J Dodson P Emsley P R Evans R M Keegan E B Krissinel A G W Leslie A McCoy S J McNicholas G N Murshudov N S Pannu E A Potterton H R Powell R J Read A Vagin and K S Wilson Acta Cryst D 2011 67 235-242

3 G Sheldrick Acta Cryst A 2008 64 112-1224 in Material Studio Accelrys Software Inc San Diego Release 50 edn 20095 N Klein C Herzog M Sabo I Senkovska J Getzschmann S Paasch M R Lohe

E Brunner and S Kaskel Phys Chem Chem Phys 2010 12 11778-117846 V Bon I Senkovska D Wallacher A Heerwig N Klein I Zizak R Feyerherm E

Dudzik and S Kaskel Micropor Mesopor Mat 20147 P Heiney University of Pennsylvania 223 edn 20108 H P K Brandenburg Crystal Impact 111g edn 20149 B Ravel and M Newville J Synchrotron Rad 2005 12 537-541

3 100 04 98 25 92 86 83 177 69 318 59 419 49 5110 43 5711 41 5912 36 64

13 Phase analysis for in situ adsorption of ethane (185 K)

Figure S12 In situ powder XRD patterns measured during adsorption of ethane (185 K) on DUT-8(Ni)

Table S6 Phase analysis of powder XRD patterns measured in situ during ethane adsorption experiment at 185 K

DUT-8(Ni) cp DUT-8(Ni) IP1 DUT-8(Ni) lp evacuated 98 0 2

1 99 0 12 97 2 13 72 28 04 25 75 05 19 81 06 12 88 07 8 92 08 8 92 09 6 88 610 3 87 1011 0 85 1512 0 74 2613 0 64 36

14 Phase analysis for in situ adsorption of ethene (169K)

Figure S13 In situ powder XRD patterns measured during adsorption of ethane (169 K) on DUT-8(Ni)

Table S7 Phase analysis of powder XRD patterns measured during in situ ethene adsorption experiment at 169K

Measuring point DUT-8(Ni) cp DUT-8(Ni) IP2 DUT-8(Ni) lp 1 98 0 22 99 0 13 99 0 14 99 0 15 87 12 16 86 13 17 46 53 18 0 71 299 0 71 2910 0 40 6011 0 38 6212 0 33 6713 0 32 6814 0 0 10015 0 96 416 0 98 217 0 99 118 0 99 1

15 PXRDs containing DUT-8(Ni) cp IP1 and C2H6DUT-8(Ni) lp

Figure S14 Experimental PXRD patterns measured during adsorption of ethane at 185 K in blue ndash XRD at pp0 =021 (DUT-8(Ni) cp) in red XRD at pp0 = 061 (IP1) in light green XRD at pp0 = 099 (mixture of C2H6DUT-8(Ni) lp and IP1)

16 PXRDs containing DUT-8(Ni) cp IP2 and C2H4DUT-8(Ni) lp

Figure S15 Experimental XRD patterns measured during adsorption of ethane at 169 K in blue XRD at pp0 = 011 (DUT-8(Ni) cp) in red XRD at pp0 = 0008 (desorption) (IP2) in light green XRD at pp0 = 092 (adsorption) (C2H4DUT-8(Ni) lp)

17 PXRDs containing IP1 and IP2 phases

Figure S16 Experimental XRD patterns of IP1 measured at pp0 = 061 185 K (ethane adsorption 185 K) in blue and of IP2 measured at pp0 = 0008 (ethylene desorption 169 K) in red

18 PXRDs containing DUT-8(Ni) as made (P4n) and N2DUT-8(Ni) (P21m)

Figure S17 Theoretical PXRD pattern of ldquoas maderdquo DUT-8(Ni) (green) experimental PXRD pattern of ldquoas maderdquo DUT-8(Ni) (blue) theoretical PXRD pattern of N2DUT-8(Ni) lp (violet) experimental PXRD pattern of N2DUT-8(Ni) lp measured at pp0 = 095 and 77K (red) (Reflection marked with asterisk belongs to the DUT-8(Ni) cp phase)

19 References

1 U Mueller N Darowski M R Fuchs R Forster M Hellmig K S Paithankar S Puhringer M Steffien G Zocher and M S Weiss J Synchrotron Rad 2012 19 442-449

2 M D Winn C C Ballard K D Cowtan E J Dodson P Emsley P R Evans R M Keegan E B Krissinel A G W Leslie A McCoy S J McNicholas G N Murshudov N S Pannu E A Potterton H R Powell R J Read A Vagin and K S Wilson Acta Cryst D 2011 67 235-242

3 G Sheldrick Acta Cryst A 2008 64 112-1224 in Material Studio Accelrys Software Inc San Diego Release 50 edn 20095 N Klein C Herzog M Sabo I Senkovska J Getzschmann S Paasch M R Lohe

E Brunner and S Kaskel Phys Chem Chem Phys 2010 12 11778-117846 V Bon I Senkovska D Wallacher A Heerwig N Klein I Zizak R Feyerherm E

Dudzik and S Kaskel Micropor Mesopor Mat 20147 P Heiney University of Pennsylvania 223 edn 20108 H P K Brandenburg Crystal Impact 111g edn 20149 B Ravel and M Newville J Synchrotron Rad 2005 12 537-541

Table S6 Phase analysis of powder XRD patterns measured in situ during ethane adsorption experiment at 185 K

DUT-8(Ni) cp DUT-8(Ni) IP1 DUT-8(Ni) lp evacuated 98 0 2

1 99 0 12 97 2 13 72 28 04 25 75 05 19 81 06 12 88 07 8 92 08 8 92 09 6 88 610 3 87 1011 0 85 1512 0 74 2613 0 64 36

14 Phase analysis for in situ adsorption of ethene (169K)

Figure S13 In situ powder XRD patterns measured during adsorption of ethane (169 K) on DUT-8(Ni)

Table S7 Phase analysis of powder XRD patterns measured during in situ ethene adsorption experiment at 169K

Measuring point DUT-8(Ni) cp DUT-8(Ni) IP2 DUT-8(Ni) lp 1 98 0 22 99 0 13 99 0 14 99 0 15 87 12 16 86 13 17 46 53 18 0 71 299 0 71 2910 0 40 6011 0 38 6212 0 33 6713 0 32 6814 0 0 10015 0 96 416 0 98 217 0 99 118 0 99 1

15 PXRDs containing DUT-8(Ni) cp IP1 and C2H6DUT-8(Ni) lp

Figure S14 Experimental PXRD patterns measured during adsorption of ethane at 185 K in blue ndash XRD at pp0 =021 (DUT-8(Ni) cp) in red XRD at pp0 = 061 (IP1) in light green XRD at pp0 = 099 (mixture of C2H6DUT-8(Ni) lp and IP1)

16 PXRDs containing DUT-8(Ni) cp IP2 and C2H4DUT-8(Ni) lp

Figure S15 Experimental XRD patterns measured during adsorption of ethane at 169 K in blue XRD at pp0 = 011 (DUT-8(Ni) cp) in red XRD at pp0 = 0008 (desorption) (IP2) in light green XRD at pp0 = 092 (adsorption) (C2H4DUT-8(Ni) lp)

17 PXRDs containing IP1 and IP2 phases

Figure S16 Experimental XRD patterns of IP1 measured at pp0 = 061 185 K (ethane adsorption 185 K) in blue and of IP2 measured at pp0 = 0008 (ethylene desorption 169 K) in red

18 PXRDs containing DUT-8(Ni) as made (P4n) and N2DUT-8(Ni) (P21m)

Figure S17 Theoretical PXRD pattern of ldquoas maderdquo DUT-8(Ni) (green) experimental PXRD pattern of ldquoas maderdquo DUT-8(Ni) (blue) theoretical PXRD pattern of N2DUT-8(Ni) lp (violet) experimental PXRD pattern of N2DUT-8(Ni) lp measured at pp0 = 095 and 77K (red) (Reflection marked with asterisk belongs to the DUT-8(Ni) cp phase)

19 References

1 U Mueller N Darowski M R Fuchs R Forster M Hellmig K S Paithankar S Puhringer M Steffien G Zocher and M S Weiss J Synchrotron Rad 2012 19 442-449

2 M D Winn C C Ballard K D Cowtan E J Dodson P Emsley P R Evans R M Keegan E B Krissinel A G W Leslie A McCoy S J McNicholas G N Murshudov N S Pannu E A Potterton H R Powell R J Read A Vagin and K S Wilson Acta Cryst D 2011 67 235-242

3 G Sheldrick Acta Cryst A 2008 64 112-1224 in Material Studio Accelrys Software Inc San Diego Release 50 edn 20095 N Klein C Herzog M Sabo I Senkovska J Getzschmann S Paasch M R Lohe

E Brunner and S Kaskel Phys Chem Chem Phys 2010 12 11778-117846 V Bon I Senkovska D Wallacher A Heerwig N Klein I Zizak R Feyerherm E

Dudzik and S Kaskel Micropor Mesopor Mat 20147 P Heiney University of Pennsylvania 223 edn 20108 H P K Brandenburg Crystal Impact 111g edn 20149 B Ravel and M Newville J Synchrotron Rad 2005 12 537-541

14 Phase analysis for in situ adsorption of ethene (169K)

Figure S13 In situ powder XRD patterns measured during adsorption of ethane (169 K) on DUT-8(Ni)

Table S7 Phase analysis of powder XRD patterns measured during in situ ethene adsorption experiment at 169K

Measuring point DUT-8(Ni) cp DUT-8(Ni) IP2 DUT-8(Ni) lp 1 98 0 22 99 0 13 99 0 14 99 0 15 87 12 16 86 13 17 46 53 18 0 71 299 0 71 2910 0 40 6011 0 38 6212 0 33 6713 0 32 6814 0 0 10015 0 96 416 0 98 217 0 99 118 0 99 1

15 PXRDs containing DUT-8(Ni) cp IP1 and C2H6DUT-8(Ni) lp

Figure S14 Experimental PXRD patterns measured during adsorption of ethane at 185 K in blue ndash XRD at pp0 =021 (DUT-8(Ni) cp) in red XRD at pp0 = 061 (IP1) in light green XRD at pp0 = 099 (mixture of C2H6DUT-8(Ni) lp and IP1)

16 PXRDs containing DUT-8(Ni) cp IP2 and C2H4DUT-8(Ni) lp

Figure S15 Experimental XRD patterns measured during adsorption of ethane at 169 K in blue XRD at pp0 = 011 (DUT-8(Ni) cp) in red XRD at pp0 = 0008 (desorption) (IP2) in light green XRD at pp0 = 092 (adsorption) (C2H4DUT-8(Ni) lp)

17 PXRDs containing IP1 and IP2 phases

Figure S16 Experimental XRD patterns of IP1 measured at pp0 = 061 185 K (ethane adsorption 185 K) in blue and of IP2 measured at pp0 = 0008 (ethylene desorption 169 K) in red

18 PXRDs containing DUT-8(Ni) as made (P4n) and N2DUT-8(Ni) (P21m)

Figure S17 Theoretical PXRD pattern of ldquoas maderdquo DUT-8(Ni) (green) experimental PXRD pattern of ldquoas maderdquo DUT-8(Ni) (blue) theoretical PXRD pattern of N2DUT-8(Ni) lp (violet) experimental PXRD pattern of N2DUT-8(Ni) lp measured at pp0 = 095 and 77K (red) (Reflection marked with asterisk belongs to the DUT-8(Ni) cp phase)

19 References

1 U Mueller N Darowski M R Fuchs R Forster M Hellmig K S Paithankar S Puhringer M Steffien G Zocher and M S Weiss J Synchrotron Rad 2012 19 442-449

2 M D Winn C C Ballard K D Cowtan E J Dodson P Emsley P R Evans R M Keegan E B Krissinel A G W Leslie A McCoy S J McNicholas G N Murshudov N S Pannu E A Potterton H R Powell R J Read A Vagin and K S Wilson Acta Cryst D 2011 67 235-242

3 G Sheldrick Acta Cryst A 2008 64 112-1224 in Material Studio Accelrys Software Inc San Diego Release 50 edn 20095 N Klein C Herzog M Sabo I Senkovska J Getzschmann S Paasch M R Lohe

E Brunner and S Kaskel Phys Chem Chem Phys 2010 12 11778-117846 V Bon I Senkovska D Wallacher A Heerwig N Klein I Zizak R Feyerherm E

Dudzik and S Kaskel Micropor Mesopor Mat 20147 P Heiney University of Pennsylvania 223 edn 20108 H P K Brandenburg Crystal Impact 111g edn 20149 B Ravel and M Newville J Synchrotron Rad 2005 12 537-541

Table S7 Phase analysis of powder XRD patterns measured during in situ ethene adsorption experiment at 169K

Measuring point DUT-8(Ni) cp DUT-8(Ni) IP2 DUT-8(Ni) lp 1 98 0 22 99 0 13 99 0 14 99 0 15 87 12 16 86 13 17 46 53 18 0 71 299 0 71 2910 0 40 6011 0 38 6212 0 33 6713 0 32 6814 0 0 10015 0 96 416 0 98 217 0 99 118 0 99 1

15 PXRDs containing DUT-8(Ni) cp IP1 and C2H6DUT-8(Ni) lp

Figure S14 Experimental PXRD patterns measured during adsorption of ethane at 185 K in blue ndash XRD at pp0 =021 (DUT-8(Ni) cp) in red XRD at pp0 = 061 (IP1) in light green XRD at pp0 = 099 (mixture of C2H6DUT-8(Ni) lp and IP1)

16 PXRDs containing DUT-8(Ni) cp IP2 and C2H4DUT-8(Ni) lp

Figure S15 Experimental XRD patterns measured during adsorption of ethane at 169 K in blue XRD at pp0 = 011 (DUT-8(Ni) cp) in red XRD at pp0 = 0008 (desorption) (IP2) in light green XRD at pp0 = 092 (adsorption) (C2H4DUT-8(Ni) lp)

17 PXRDs containing IP1 and IP2 phases

Figure S16 Experimental XRD patterns of IP1 measured at pp0 = 061 185 K (ethane adsorption 185 K) in blue and of IP2 measured at pp0 = 0008 (ethylene desorption 169 K) in red

18 PXRDs containing DUT-8(Ni) as made (P4n) and N2DUT-8(Ni) (P21m)

Figure S17 Theoretical PXRD pattern of ldquoas maderdquo DUT-8(Ni) (green) experimental PXRD pattern of ldquoas maderdquo DUT-8(Ni) (blue) theoretical PXRD pattern of N2DUT-8(Ni) lp (violet) experimental PXRD pattern of N2DUT-8(Ni) lp measured at pp0 = 095 and 77K (red) (Reflection marked with asterisk belongs to the DUT-8(Ni) cp phase)

19 References

1 U Mueller N Darowski M R Fuchs R Forster M Hellmig K S Paithankar S Puhringer M Steffien G Zocher and M S Weiss J Synchrotron Rad 2012 19 442-449

2 M D Winn C C Ballard K D Cowtan E J Dodson P Emsley P R Evans R M Keegan E B Krissinel A G W Leslie A McCoy S J McNicholas G N Murshudov N S Pannu E A Potterton H R Powell R J Read A Vagin and K S Wilson Acta Cryst D 2011 67 235-242

3 G Sheldrick Acta Cryst A 2008 64 112-1224 in Material Studio Accelrys Software Inc San Diego Release 50 edn 20095 N Klein C Herzog M Sabo I Senkovska J Getzschmann S Paasch M R Lohe

E Brunner and S Kaskel Phys Chem Chem Phys 2010 12 11778-117846 V Bon I Senkovska D Wallacher A Heerwig N Klein I Zizak R Feyerherm E

Dudzik and S Kaskel Micropor Mesopor Mat 20147 P Heiney University of Pennsylvania 223 edn 20108 H P K Brandenburg Crystal Impact 111g edn 20149 B Ravel and M Newville J Synchrotron Rad 2005 12 537-541

16 PXRDs containing DUT-8(Ni) cp IP2 and C2H4DUT-8(Ni) lp

Figure S15 Experimental XRD patterns measured during adsorption of ethane at 169 K in blue XRD at pp0 = 011 (DUT-8(Ni) cp) in red XRD at pp0 = 0008 (desorption) (IP2) in light green XRD at pp0 = 092 (adsorption) (C2H4DUT-8(Ni) lp)

17 PXRDs containing IP1 and IP2 phases

Figure S16 Experimental XRD patterns of IP1 measured at pp0 = 061 185 K (ethane adsorption 185 K) in blue and of IP2 measured at pp0 = 0008 (ethylene desorption 169 K) in red

18 PXRDs containing DUT-8(Ni) as made (P4n) and N2DUT-8(Ni) (P21m)

Figure S17 Theoretical PXRD pattern of ldquoas maderdquo DUT-8(Ni) (green) experimental PXRD pattern of ldquoas maderdquo DUT-8(Ni) (blue) theoretical PXRD pattern of N2DUT-8(Ni) lp (violet) experimental PXRD pattern of N2DUT-8(Ni) lp measured at pp0 = 095 and 77K (red) (Reflection marked with asterisk belongs to the DUT-8(Ni) cp phase)

19 References

1 U Mueller N Darowski M R Fuchs R Forster M Hellmig K S Paithankar S Puhringer M Steffien G Zocher and M S Weiss J Synchrotron Rad 2012 19 442-449

2 M D Winn C C Ballard K D Cowtan E J Dodson P Emsley P R Evans R M Keegan E B Krissinel A G W Leslie A McCoy S J McNicholas G N Murshudov N S Pannu E A Potterton H R Powell R J Read A Vagin and K S Wilson Acta Cryst D 2011 67 235-242

3 G Sheldrick Acta Cryst A 2008 64 112-1224 in Material Studio Accelrys Software Inc San Diego Release 50 edn 20095 N Klein C Herzog M Sabo I Senkovska J Getzschmann S Paasch M R Lohe

E Brunner and S Kaskel Phys Chem Chem Phys 2010 12 11778-117846 V Bon I Senkovska D Wallacher A Heerwig N Klein I Zizak R Feyerherm E

Dudzik and S Kaskel Micropor Mesopor Mat 20147 P Heiney University of Pennsylvania 223 edn 20108 H P K Brandenburg Crystal Impact 111g edn 20149 B Ravel and M Newville J Synchrotron Rad 2005 12 537-541

18 PXRDs containing DUT-8(Ni) as made (P4n) and N2DUT-8(Ni) (P21m)

Figure S17 Theoretical PXRD pattern of ldquoas maderdquo DUT-8(Ni) (green) experimental PXRD pattern of ldquoas maderdquo DUT-8(Ni) (blue) theoretical PXRD pattern of N2DUT-8(Ni) lp (violet) experimental PXRD pattern of N2DUT-8(Ni) lp measured at pp0 = 095 and 77K (red) (Reflection marked with asterisk belongs to the DUT-8(Ni) cp phase)

19 References

1 U Mueller N Darowski M R Fuchs R Forster M Hellmig K S Paithankar S Puhringer M Steffien G Zocher and M S Weiss J Synchrotron Rad 2012 19 442-449

2 M D Winn C C Ballard K D Cowtan E J Dodson P Emsley P R Evans R M Keegan E B Krissinel A G W Leslie A McCoy S J McNicholas G N Murshudov N S Pannu E A Potterton H R Powell R J Read A Vagin and K S Wilson Acta Cryst D 2011 67 235-242

3 G Sheldrick Acta Cryst A 2008 64 112-1224 in Material Studio Accelrys Software Inc San Diego Release 50 edn 20095 N Klein C Herzog M Sabo I Senkovska J Getzschmann S Paasch M R Lohe

E Brunner and S Kaskel Phys Chem Chem Phys 2010 12 11778-117846 V Bon I Senkovska D Wallacher A Heerwig N Klein I Zizak R Feyerherm E

Dudzik and S Kaskel Micropor Mesopor Mat 20147 P Heiney University of Pennsylvania 223 edn 20108 H P K Brandenburg Crystal Impact 111g edn 20149 B Ravel and M Newville J Synchrotron Rad 2005 12 537-541